High internal resistance that reduces the power produced in the microbial fuel cells (MFCs) is mainly due to the low electron transfer between the bacterial catalysts and the anode/cathode. In this study, a bulk modified Graphite Polyester composite electrodes (GPECE) doped with metal salts (MS-GPECE) were prepared by casting. Crystallinity, surface morphology, chemical composition and electrochemical properties of all modified electrodes were investigated. Influence of redox behavior of electrodes suited to bacterial metabolism and enhanced biofilm formation have been examined. A laboratory-scale H-shaped Pseudomonas catalyzed microbial fuel cell (MFC) was investigated with different metal doped Graphite Polyester composite electrodes, for its performance in decolorizing synthetic wastewater containing azo dye methyl orange. Among the different combinations of electrodes were tested in MFC, the best performing MFC with the highest power density (1575 +/- 223.26 mu W/m(2)) was seen with Ni-GPECE as the cathode and graphite block as an anode and simultaneous increase in decolorization (89 +/- 1.41%) was also observed. These studies have suggested that the MFC technology can discharge the dual duty of degrading the azo dyes and simultaneous power production.